Direct esterification of glycosides with fatty acids



DIRECT ESTERIFICATION OF GLY'COSIDES WITH FATTY ACIDS John P. Gibbons, Pittsburgh, Pa., assignor to Corn Products Refining Company, New York, N. Y., a corporation of New Jersey No Drawing. Application June 21, 1952, SerialNo. 294,937

22 Claims. 01. 260-210) This invention relates to the production of esters of glycosides, and more particularly to the production of fatty acid esters of glycosides, by direct esterification of a glycoside with a fatty acid.

The classical method for the preparation of fatty acid esters of glycosides employs the reaction of a glycoside with the fatty acid halide, usually in the presence of an excess of an organic base, such as quinoline or pyridine, which combines with the hydrogen halide formed by the reaction. Upon completion of the esterification, the reaction mixture is poured into cold water, from which the ester is extracted with a water immiscible solvent. The crude ester is then obtained from the extract by distilling off the solvent.

This method is costly for commercial production of fatty acid esters of glycosides, because of the lengthy processing and numerous steps required, in addition to the fact that the fatty acid halides are considerably more expensive than the free fatty acid.

However, direct esterification of glycosides by the free fatty acids has been found to be unfeasible by the usual methods employed for the direct esterification of alcohols. These procedures employ an acid catalyst, e. g. sulfuric or hydrochloric acids, to bring about the reaction of the alcohol with the fatty acid. When it is attempted to esterify glycosides directly by such methods, extensive degradation of the glycosides occurs, as evidenced by excessive carmelization and, eventually, complete carbonization of the reaction mixture, resulting in extremely poor yields at best.

It has now been discovered that glycosides can be directly esterified with free fatty acids, without appreciable destruction of the glycoside and with good yields of the esters, by heating a mixture of the glycoside and free fatty acid under controlled conditions without a catalyst. It was very surprising that a satisfactory yield of ester could be obtained without a catalyst, inasmuch as direct esterification ordinarily requires the use of a catalyst, usually a strong acid. Furthermore, it also was rather astonishing that simple derivatives of sugars, such as the glycosides, would withstand the temperatures employed without extensive degradation, since the sugars are notoriously sensitive to elevated temperatures, being rapidly degraded thereby.

Accordingly, it is an object of this invention to provide a method for the production of fatty acid esters of glycosides by direct esterification of glycosides with free'fatty acids. Another object of this invention is to provide a process for the production of glycoside esters of high quality, in good yields, and more economically than heretofore was possible. A further object of this invention is the production of fatty acid esters of glycosides by direct esterification of the glycosides with free fatty acids without the use of a catalyst. Other objects and advantages will appear hereinafter.

The present invention comprises heating the free fatty acid with the glycoside, without a catalyst, at temperaatent OfiFice 2,759,922 Patented Aug. 21, 1956 tures within the range of about 160 C. to 300 C. until the desired degree of esterification has been obtained.

Diesters, triesters, and tetra esters may be prepared according to this invention by suitable control of the reaction time, temperature and/or ratio of reactants.

Glycosides of the hexoses, pentoses, and other sugars may be employed in the process of this invention. The glycosides employed, advantageously, should be of high purity, containing substantially no free mineral acid and only small amounts of free sugars, if any, in order to avoid side reactions resulting in extremely dark colored products.

The fatty acids suitable for use in this invention are preferably those which contain 6 to 20 carbon atoms in their aliphatic chains. Both saturated and unsaturated fatty acids, in the pure state or as mixtures such as are obtained by the saponification of vegetable oils, as well as synthetic mixtures of fatty acids are suitable. Some examples of suitable fatty acids are caproic, lauric, palmitic, oleic, stearic, linoleic, and linolenic acids, as well as the fatty acids of dehydrated castor oil, linseed oil, corn oil and soy bean oil. Obviously, if mixtures of fatty acids are employed, mixed esters will be obtained.

The ratio of glycoside to free fatty acid employed in the reaction is not critical, except that the amount of free fatty acid must be, obviously, at least equivalent to that theoretically required to produce the desired degree of esterification; i. e. if a tetra ester is desired, at least 4 mols of fatty acid will be necessary. Similarly if a dior triester is desired, at least 2 or 3 mols, respectively, of fatty acid must be employed to substantially completely convert the glycoside to the corresponding ester. However, an excess of fatty acid may be used, if desired.

When an excess of fatty acid over that theoretically required to produce the desired ester is employed, the degree of esterification is controlled by suitable choice of reaction conditions, such as temperature and reaction time, which are interdependent variables.

The temperature utilized to accomplish the esterification is important, since too high a temperature tends to produce side reactions, whereas too low a temperature results in extremely slow rates of esterification. Temperatures within the range of about 160 C. to about 300 C., give good yields of esters of desirable quality within a reasonable length of time and, therefore, are preferred.

In many cases the color of the final product may be improved by maintaining the temperature at the beginning of the reaction at the lower end of the range and increasing the temperature, preferably stepwise, as the esterification proceeds.

For example, the temperature may be maintained below 200 C. until the esterification is about 50% completed, then above 200 C. for the remainder, or the temperature may be maintained within the lower portion of the aforesaid range until the esterification is approxi mately completed, and thereafter increased, preferably to about 230 to 250 C., until the esterification is completed. The latter procedure is especially suitable when preparing a tetra ester. The progress of the esterification may conveniently be followed by measuring the amount of water liberated in the reaction, which will be discussed more fully hereinafter.

Since esterification is a reversible reaction in the presence of water, and water is one of the products formed in a direct esterification, it is advantageous to provide means for removal of the water of esterification as it is formed in orderto force the esterification to substantial completion. It is also advantageous to agitate the reaction mixture during the esterification, as this tends to increase somewhat the esterification rate and also to give a more uniform heat distribution throughout the reaction mixture and thereby prevent or minimize local overheating with its resultant deterioration in quality of the product.

The removal of the water is facilitated, and hence the reaction rate increased, by the application of a slight vacuum to the system. The removal of water is conveniently accomplished by the addition to the reaction mixture of a substance which forms an azeotrope with water, e. g. benzene, toluene, or xylene. Such addition also accelerates the reaction rate.

Passage of an inert gas such as nitrogen or carbon dioxide over the surface of the reaction mixture tends to produce final products of improved color, although this is not essential, particularly when an azeotrope is employed for removal of water.

The glycoside esters produced by the process of this invention are particularly useful as drying oils, for example in the production of varnishes.

The following examples, which are intended as typical and informative only and not in a limiting sense, will further illustrate the invention:

Example 1 Twelve hundred grams (equivalent to 4.175 mols) of linseed oil fatty acids (acid No. 199.5) and 203 grams of methyl alpha-D-glucoside (equivalent to 1.045 mols) were placed in a three liter 3-necked flask equipped with a water distilling trap (Dean-Stark tube) attached to a reflux condenser, thermometer, gas inlet tube and a mechanical stirrer. While agitating and passing nitrogen over the reactants the mixture was heated to 185 C. as rapidly as possible by means of a hemispherical electric mantle. At this point xylene was added through the condenser to fill the trap and into the reaction mixture to remove the water of esterification by entrainment. The temperature was maintained between 185 C. and 200 C. for 0.75 hour, then at 215 C. for 3.3 hours and finally at 230 C. for 6 hours. After removing the xylene by jetting with nitrogen and cooling to room temperature, the yield was 1333 grams of a red oil having an acid number of 28.6 (85.7% ester), a saponification number of 181, a Hellige color of 15 and a Gardner viscosity at 25 C. of 100 centipoises.

Example 2 In an apparatus similar to that described in Example 1, 197.5 grams (equivalent to 1 mol) of lauric acid (acid No. 284) and 48.5 grams of methyl alpha-D-glucoside (0.25 mol) was heated rapidly to 170 C. while stirring and sparging with carbon dioxide. Xylene was then added to azeotropically remove the water of esterification. The temperature was maintained between 185 C. and 200 C. for 5 hours, then at 225 C. to 235 C. for an additional 6 hours. After jetting off the xylene with carbon dioxide and cooling to room temperature the yield was 225 grams of a dark colored oil. This material was dissolved in benzene and decolorized by refluxing for 2 hours with 23 grams of activated carbon (Nuchar W). After filtering off the carbon and removing the benzene under vacuum, the product weighed 199.6 grams and had an acid number of 35 (87.7% ester), a saponification number of 251 and a Hellige color of 8. After standing at room temperature this material solidified and had a melting point of 38 C. to 43 C.

Example 3 In an apparatus similar to that described in Example 1, 149 grams (equivalent to 1.25 mols) of caproic acid (acid No. 470) and 48.5 grams of methyl alpha-D-glucoside (equivalent to 0.25 mol) was heated rapidly to 166 C. while stirring in an atmosphere of carbon dioxide. Xylene was added to entrain the water of esterification. The reaction mass was heated between 180 C. and 200 C. for 7 hours and then between 225 C. and 235 C. for an additional 2 hours. The xylene and excess caproic acid was jetted off with carbon dioxide at 235 C. After cooling to room temperature the product was dissolved in 500 ml. of benzene and decolorized by refluxing with 20 grams of activated carbon (Nuchar W) for 1 hour. The carbon was filtered off and the benzene removed from the filtrate by distillation. The yield was 125.5 grams of a tan oil having an acid number of 4.7 (99% ester), a saponification number of 358, a Hellige color of 8, and a Gardner viscosity at 25 C. of centipoises.

Example 4 In an apparatus similar to that described in Example 1, 296.3 grams (equivalent to 1.5 mols) of a lauric acid (acid No. 284) and 144.5 grams of methyl alpha-D-glucoside (equivalent to 0.745 mol) was heated rapidly to 160 C. while agitating and sparging with carbon dioxide. Xylene was then added to entrain the water of esterification. The reaction mixture was heated at C. to 202 C. for 8 hours, then at 215 C. for an additional 3 hours. The xylene was jetted off with carbon dioxide and the contents cooled to room temperature. The product was dissolved in 1000 ml. of benzene and treated under reflux for 1 hour with 31 grams of activated carbon (Nuchar W). The carbon was removed by filtration and the benzene distilled off in vacuo. The yield was 413.5 grams of product with an acid number of 12.2 (95.7% ester), a saponification number of 199, a Hellige color of 12 and a Gardner viscosity at 25 C. of 884 centipoises.

Example 5 In an apparatus similar to that described in Example 1, 293 grams (equivalent to 1 mol) of dehydrated castor oil fatty acids (acid No. 191.3) and 48.5 grams of methyl alpha-D-glucoside (equivalent to 0.25 mol) was heated rapidly to 164 C. while stirring and sparging with carbon dioxide. At this point xylene was added to azeotropically remove the water formed. The temperature of the reaction was maintained between 198 C. and 207 C. for 8 hours, then at 230 C. for 2 hours and finally at 255 C. to 261 C. for 2 hours. After jetting off the xylene with carbon dioxide and cooling to room temperature the product weighed 323 grams. This ester had an acid number of 29.3 (84.7% ester), a saponification number of 179, a Hellige color of 12 and a Gardner viscosity at 25 C. of 275 centipoises.

Example 6 In an apparatus similar to that described in Example 1, 272.5 grams (equivalent to 1 mol) of soya fatty acids (acid No. 206) and 48.5 grams of methyl alpha-D- glucoside was heated rapidly to 160 C. with stirring and carbon dioxide sparging. Xylene was then added as a water entrainer and the reaction mass maintained between C. and 206 C. for 17 hours. The xylene was jetted off with carbon dioxide and the reaction product cooled to room temperature. The yield was 306.6 grams of a red oil having an acid number of 37.3 (81.9% ester), a saponification number of 188.0, a Hellige color of 17 and a Gardner viscosity at 25 C. of 110 centipoises.

Example 7 In an apparatus similar to that described in Example 1, 282.5 grams (equivalent to 1 mol) of oleic acid (acid No. 199) and 48.5 grams of methyl alpha-D-glucoside (equivalent to 0.25 mol) was heated rapidly to 164 C. With stirring and carbon dioxide sparging. Xylene was added to entrain the water of esterification and the temperature was held between 190 C. and 210 C. for 4 hours and then between 230 C. and 240 C. for an additional 8 hours. After removing the xylene by jetting with carbon dioxide and cooling to room temperature the product weighed 315 grams. This material was dissolved in a liter of benzene and decolorized by refluxing for 4 hours with 48 grams of activated carbon (Nuchar After removing the carbon by filtration and stripping oif the benzene in vacuo 289.2 grams of a red oil was obtained which had an acid number of 26.8 (86.5%

ester), a saponification number of 182.5, a Hellige color of 17 and a Gardner viscosity of.140 centipoises.

Example 8 In an apparatus similar to that described in Example 1, 423.8 grams (equivalent to 1.5 mols) of oleic acid (acid No. 198.3) and 97 grams of methyl alpha-D-glucoside (equivalent to 0.5 mol) was heated rapidly to 185 C. while stirring in a carbon dioxide atmosphere. Xylene was then added to entrain the water of reaction. The temperature was maintained between 185 C. and 201 C. for 3 hours and then between 210 C. and 220 C. for 5 hours. After jetting ofi the xylene with carbon dioxide and cooling to room temperature, the yield was 495 grams of a red oil with an acid number of 13.6 (93.1% ester), a saponification number of 168.5 and a Hellige color of 18.

Example 9 In a one liter flask equipped as described in Example 1, 282 grams of linseed oil fatty acids (acid No. 199-equivalent to 1.0 mol) and 48.5 grams of methyl alpha-D-glucoside (0.25 mol) was heated rapidly to 165 C. Xylene was then added as an azeotropic water removal agent and the temperature raised to 190 C. The heating cycle was maintained at 193 C.to 197 C. for 3 hours, at 208 C. to 214 C. for 3 hours, at 230 C. to 234 C. for 2 hours, and finally at 250 C. to 260 C. for 2 hours. After stripping off the xylene, 316 grams of a dark red oil was recovered. The acid number of the ester was 30.5 (84.7% ester), a saponification value of 180, the Hellige color 18, and the Gardner viscosity 200 centipoises.

Example 10 To a one liter flask equipped with a stirrer, thermometer, carbon dioxide inlet, and a water removal outlet connected to a source of vacuum was charged 282 grams of linseed oil fatty acids (acid No. 199equivalent to 1.0 mol) and 48.5 grams of methyl alpha-D-glucoside (0.25 mol). The mixture was heated rapidly to 165 C. while sparging with carbon dioxide, and a vacuum of 100150 mm. Hg was applied to facilitate the removal of Water of esterification. Heating was continued at 187 C. to 195 C. for 3 hours, at 210 C. to 214 C. for 3 hours, then at 230 C. to 233 C. for 3 hours, and finally at 250 C. to 252 C. for 2 hours. A yield of 301.5 grams of a dark red oil was obtained having an acid number of 23.1 (884 ester), a saponification value of 182.5, a Hellige color of 18+, and a Gardner viscosity of 250 centipoises.

Example 11 In an apparatus similar to that described in Example 1, 286 grams (equivalent to 1.0 mol) of linseed oil fatty acids (acid No. 196.5) and 48.5 grams (equivalent to 0.25 mol) of methyl alpha-D-glucoside, were heated rapidly to 160 C. in an atmosphere of carbon dioxide, and xylene was added to entrain the water of esterification. Heating was continued at 190 C. to 195 C. for 3 hours, then at 215 C. for 2 hours and mially at 230 C. for 3 hours. At this point the reaction was stopped, and the xylene was jetted off with carbon dioxide during the cooling cycle. The resulting dark red oil weighed 319 grams, had an acid number of 44.4 (77.4% ester), a saponification value of 177, a Hellige color of 16, and a Gardner viscosity of 100 centipoises.

A duplicate esterification was carried out using the same technique as described above. The product weighed 318.4 grams and had the following properties: an acid number of 44.5 (77.4% ester), a saponification value of 177, a Hellige color of 16, and a Gardner viscosity of 120 centipoises.

Example 12 In an apparatus similar to that described in Example 1, 286 grams (equivalent to 1.0 mol) of linseed oil fatty acids (acid No. 196.5) and 48.5 grams (equivalent to 0.25 mol) of methyl alpha-D-glucoside were heated rapid- 1y to 230 C. while sparging with carbon dioxide. Xylene was added, as an azeotropic water removal agent, and the reaction was maintained at 230 C. for 4 hours. The xylene was then removed from the reaction by jetting with carbon dioxide while the product was allowed to cool to room temperature. A dark colored oil weighing 320.8 grams was recovered having an acid number of 52.6 (73.2% ester), a saponification value of 178, a Hellige color of 18, and a Gardner viscosity of centipoises.

A duplicate experiment was carried out employing the same technique as described above. The resultant product weighed 317.8 grams, had an acid number of 51.8

(73.6% ester), a saponification value of 180, a Hellige color of 18, and a Gardner viscosity of centipoises.

Example 13 In an apparatus similar to that described in Example 1, 286 grams (equivalent to 1 mol) of linseed fatty acids (acid No. 196.5 and 97 grams of methyl alpha-D-glucoside (0.5 mol) was heated rapidly to C. while stirring and sparging with carbon dioxide. At this point xylene was added and the temperature raised to 200 C. and held for 7 hours. After removing the xylene by jetting with carbon dioxide, 371 grams of a dark red oil was obtained which had an acid number of 24 (equivalent to 12.2% free fatty acids) and a saponification number of'146. The product was dissolved in 500 ml. of ethyl ether and extracted with five 100 ml. portions of water. The combined aqueous extractions on evaporation to dryness yielded 6.5 grams of a solid material which on crystallization from methanol melted at 163 C. to 165 C. (melting point of methyl alpha-D-glucoside is 165 C.). The unreacted methyl alpha-D-glucoside (6.5 grams) is equivalent to 6.8 per cent of the original charge.

Example 14 In an apparatus similar to that described in Example 1. 1138.1 grams (equivalent to 4 mols) of linseed oil fatty acids (acid No. 197.2) and 194.2 grams of mixed methyl alphaand beta-D-glucosides (equivalent to 1 mol) was heated rapidly to 144 C. while stirring in an atmosphere of carbon dioxide. Xylene was added to entrain the water of esterification and the temperature raised to 190 C. in 30 minutes. The temperature was maintained between 190C. and 205 C. for 5.5 hours, then at 215 C. for an additional 4.25 hours. The xylene was jetted off with carbon dioxide and the temperature raised to 300 C. and held for 1 hour to body the oil. After cooling to room temperature the yield was 1238.9 grams of a viscous red oil with an acid number of 6.2 (96.8% ester), a saponification number of 183, a Hellige color of 18 and a Gardner viscosity at 25 C. of 1760 centipoises.

Example 15 In an apparatus similar to that described in Example 1, 139.9 grams (equivalent to 0.5 mol) of linseed oil fatty acids (acid No. 200.5) and 24.3 grams (equivalent to 0.125 mol) ofmethyl beta-D-glucoside (containing 0.7% reducing sugar M. P. 104 C.-106 C.) was heated rapidly to 150 C. while stirring in an atmosphere of carbon dioxide. Xylene was added at this point to azeotrope the water of esterification. The temperature was maintained between C. and 205 C. for 7 hours, then the xylene was jetted off with carbon dioxide. After cooling to room temperature the yield was 159.2 grams of a red oil with an acid number of 59.5 (70.3% ester), a saponification number of 181, a Hellige color of 18 and a Gardner viscosity at 25 C. of 120 centipoises.

7 Example 16 In an apparatus similar to that described in Example 1, 139.9 grams (equivalent to 0.5 mol) of linseed oil fatty acids (acid No. 200.5) and 43.4 grams (equivalent to 0.125 mol) of a 60% aqueous solution of mixed ethyl-D-glucosides (26 grams of solid mixed ethyl-D-glucosides) was heated over a period of 50 minutes to 170 C. with stirring and carbon dioxide sparging. Xylene was added to entrain the water of esterification. The temperature was maintained between 178 C. and 196 C. for 6 hours, then the xylene was jetted off with carbon dioxide and the reaction mass cooled to room temperature. The yield was 159.9 grams of a dark red oil with an acid number of 67.2 (66.5% ester), a saponification number of 178, a Hellige color of 18+ and a Gardner viscosity at 25 C. of 100 centipoises.

Example 17 In an apparatus similar to that described in Example xylene was added to replace the toluene as an azeotropic water removal agent. Temperatures were maintained at 194 C. to 198 C. for 2 hours, at 215 C. to 218 C. for 3 hours, and finally at 225 C. to 229 C. for an additional hours. After removal of the xylene by jetting with carbon dioxide and cooling to room temperature, the yield was 129 grams of a dark-colored oil with an acid number of 29.9 (85.0% ester), a saponification value of 173, a Hellige color of 18+, and a Gardner viscosity of 135 centipoises.

Example 18 In an apparatus similar to that described in Example 1, and using the sametechnique outlined in Example 14, 72.7 grams of linseed oil fatty acids (acid No. 199 equivalent to 0.258 mol), 14.2 grams of allyl alpha-D- glucoside (M. P. 90l00 C., reducing sugar 0.71%, equivalent to 0.0645 mol), and about 50 ml of toluene were heated slowly to 190 C. in an atmosphere of carbon dioxide. Initial water of esterification began to distill over at 160 C. to 165 C. The heating cycle was held at 194 C. to 196 C. for 2 hours, then at 211 C. to 220 C. for 5 hours, and finally 225 C. to 230 C. for 3 hours. After jetting olf the xylene with carbon dioxide and cooling the product to room temperature, the yield was 81 grams of a dark-colored oil with an acid number of 32.2 (83.8% ester), a saponification value of In an apparatus similar to that described in Example 1, 80.0 grams of linseed oil fatty acids (acid No. 196.5- equivalent to 0.28 mol) and 14.8 grams of methyl alpha- D-galactoside hydrate (equivalent to .07 mol) was heated rapidly to 160 C. in a carbon dioxide atmosphere. After adding xylene to azeotrope the water of esterification, the reaction was maintained at 190 C. to 195 C. for 6.3 hours and then at 200 C. to 205 C. for 3.7 hours. The xylene was jetted off with carbon dioxide while cooling the reaction. A dark red oil weighing 90.9 grams was recovered which had an acid number of 50.1 (74.5% ester), a saponification number of 179, a Hellige color of 18+, and a Gardner viscosity of 100 centipoises.

Example 20 In an apparatus similar to that described in Example 1, 80.0 grams of linseed oil fatty acids (acid No. 196.5-

iii

equivalent to 0.28 mol) and 15.2 grams of methyl beta- L-arabinoside (equivalent to .093 mol) was heated rapidly to 160 C. in an atmosphere of carbon dioxide. Xylene was added to entrain the water of esterification, and the reaction was carried out according to the following heating cycle: 190 C. to 195 C. for 4 hours followed by 200 C. to 207 C. for an additional 5 hours. The xylene was removed by jetting with carbon dioxide while the reaction was allowed to cool. The resulting darkcolored oil weighed grams and had an acid number of 54.6 (72.2% ester), a saponification number of 172, a Hellige color of 18+, and a Gardner viscosity of centipoises.

I claim:

1. A process for the production of fatty acid esters of glycosides, which comprises reacting a glycoside from the group consisting of methyl glucoside, ethyl glucoside, beta-ethoxyethyl-beta-D-glucoside, allyl glucoside, methyl galactoside, methyl arabinoside with a free fatty acid containing 6 to 20 carbon atoms in the aliphatic chain, at a temperature within the range of about C. to about 300 C. until the desired degree of esterification is attained.

2. Process according to claim 1, wherein the water of esterification is removed from the reaction mixture during the esterification.

3. Process according to claim 2, wherein the water of esterification is removed by a vacuum applied to the system.

4. Process according to claim 2, wherein the water of esterification is removed by azeotropic distillation.

5. Process according to claim 1, wherein the temperature is gradually increased during the esterification.

6. Process according to claim 1, wherein the temperature is increased stepwise during the reaction.

7. Process according to claim 1, wherein said free fatty acid is a mixture of free fatty acids obtained by saponification of a vegetable oil.

8. Process according to claim 7, wherein said mixture of free fatty acids is linseed oil fatty acids.

9. Process according to claim 7, wherein said mixture of free fatty acids is soybean oil fatty acids.

10. Process according to claim 7, wherein said mixture of free fatty acid is dehydrated castor oil fatty acids.

11. Process according to claim 1, wherein said free fatty acid is oleic acid.

12. Process according to claim 1 wherein said free fatty acid is stearic acid.

13. Process for the production of a fatty acid ester of methyl glucoside, comprising heating a mixture of the free fatty acid and methyl glucoside, at a temperature within the range of about 160 C. to about 300 C., with continuous removal of water of esterification from the reaction mixture during said heating, until the desired degree of esterification has been attained.

14. Process according to claim 12, wherein the water of esterification is removed azeotropically.

15. Process according to claim 12, wherein the water of esterification is removed by means of a vacuum.

16. Process according to claim 12, wherein the esterification is carried out in an inert atmosphere.

17. Process for the production of linseed oil fatty acids tetra ester of methyl glucoside, comprising heating a mixture of methyl glucoside, linseed oil fatty acids, and xylene, at a temperature increased stepwise within the range of about C. to about 230 C. for about 10 hours, under an atmosphere of nitrogen; the water of esterification being continuously removed by azeotropic distillation with the xylene; the molar ratio of linseed oil fatty acids to methyl glucoside being at least 4:1.

18. Process for the production of the dehydrated castor oil fatty acids tetra ester of methyl glucoside, comprising heating a mixture of dehydrated castor oil fatty acids, methyl glucoside, and xylene, at a temperature increased stepwise within the range of about 198 C. to about 261 C. for about 12 hours, under an atmosphere of carbon dioxide; the water of esterification being continuously removed by azeotropic distillation with the xylene; the molar ratio of dehydrated castor oil fatty acids to methyl glucoside being at least 4:1.

19. Process for the production of the soya fatty acids tetra ester of methyl glucoside, comprising heating a mixture of soya fatty acids, methyl glucoside, and xylene, at a temperature of about 190 C. to about 205 C. for about 17 hours under an atmosphere of carbon dioxide; the water of esterification being removed by azeotropic distillation with the xylene; the molar ratio of said soya fatty acids to said methyl glucoside being at least 4: 1.

20. Process for the production of the oleic acid tetra ester of methyl glucoside, comprising heating a mixture of oleic acid, methyl glucoside, and xylene, at a temperature increased stepwise within the range of about 190 C. to about 240 C. for about 12 hours under an atmosphere of carbon dioxide; the Water of esterification being removed by azeotropic distillation with the xylene; the molar ratio of said oleic acid to said methyl glucoside being at least 4: 1.

21. Process for the production of the oleic acid triester of methyl glucoside, comprising heating a mixture of oleic acid, methyl glucoside, and xylene, at a temperature increased stepwise within the range of about 185 C. to about 220 C. for about 8 hours; the water of esterification being continuously removed by azeotropic distillation with the xylene; the molar ratio of said oleic acid to said methyl glucoside being at least 3:1.

22. Process for the production of the linseed oil fatty References Cited in the file of this patent UNITED STATES PATENTS 981,178 Diesser Jan. 10, 1911 1,668,945 Clarke et al. May 8, 1928 2,013,034 Cox et al. Sept. 3, 1935 2,077,371 Rheineck et a1. Apr. 13, 1937 2,122,716 Graves July 5, 1938 FOREIGN PATENTS 487,020 Great Britain June 14, 1938 OTHER REFERENCES Chwala: A. P. 0., Ser. No. 283,323, publ. April 20, 1943.

Wolfi et al.: J. Am. Oil. Chem. Soc., 25 (1948), pages 258460.

Stacey et al.: Nature, 164, page 705' (1949).

Gibbons & Janke: J. Am. Oil. Chem. Soc., 29 (1952), pages 467-469.

Whistler et al.: Polysaccharide Chemistry, page 76, (1953). 

